Acid salt form of deae cellulosic fabric providing built-in catalysis for the reaction with aminoplasts

ABSTRACT

DIETHYLAMINOETHYLATED CELLULOSIC FIBERS, THE DIETHYLAMINOETHYL GROUPS OF WHICH ARE IN AN ACID SALT FORM, PROVIDE A BUILT-IN CATALYST FOR THE REACTION OF SAID FIBERS WITH METHYLOLATED NITROGEN CONTAINING CROSS-LINKING AGENTS WITH WHICH SAID FIBERS ARE CONTACTED.

United States Patent 01 fice 3,579,289 Patented May 18, 1971 3,579,289 ACID SALT FORM OF DEAE CELLULOSIC FABRIC PROVIDING BUILT-IN CATALYSIS FOR THE REACTION WITH AMINOPLASTS Donald M. Soignet, Metairie, and Ruth R. Benerito, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Jan. 16, 1970, Ser. No. 3,514 Int. Cl. C081) 11/20; D06m 13/40, 13/54 US. Cl. 8-1165 7 Claims ABSTRACT OF THE DISCLOSURE Diethylaminoethylated cellulosic fibers, the diethylaminoethyl groups of which are in an acid salt form, provide a built-in catalyst for the reaction of said fibers with methylolated nitrogen containing cross-linking agents with which said fibers are contacted.

A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

It iswell known in the art that the cellulose hydroxyls will react with substituted cyclic ureas in the presence of a catalyst. These catalysts, which are added to the reagent solution, are usually ammonium salts (Cooke, J. F., Roth, P. B., Salsbury, J. M., Switlyk, G., and van Loo, W. 1., Tex. Res. J. 27, 150-165, 1957), or metal salts (Marsh, J. T., Tex. Mfr., 86, 113, 1960). Once, however, the solution of catalyst and reagent are padded onto the fabric and the fabric dried at low temperatures (below 70 C.), the reaction between the reagent and the cellulose will proceed rapidly on the application of heat or at a somewhat slower rate at room temperature. This negates the possibility of padding the reagent and catalyst on a fabric and thenstoring it for long periods of time before curing.

The process described in this invention differs from the art in that the catalyst is incorporated first as an integral part of the cellulosic material and thus need not be added to the reagent solution. The fabric padded in this manner will not react with the reagent solution until curing temperatures are attained. It is then possible to store the reagent on the fabric without fear of reaction. The reaction can be initiated when curing temperatures are reached.

In carrying out the preferred process of this invention, cellulosic fabric is treated with a 20% aqueous solution of 2-chloroet-hyldiethylamine hydrochloride and cured in 8% sodium hydroxide at 95 C. according to the method of Soignet and Benerito (Tex. Res. 1., 37, 1001-1003, 1967). The diethylaminoethylated (DEAE) cellulose thus produced is soaked in 0.1 N sodium hydroxide to convert it to the base form. This fabric is then converted to the desired acid salt by soaking in a 0.5 N solution of the corresponding acid. Unbound acid is then washed out and the fabric is then padded to a 100% wet pickup with an aqueous solution of the desired substituted cyclic urea and dried at 60 C. for about 7 minutes. The fabric can now be cured at elevated temperatures or set aside and cured at some later date.

Cellulosic materials such as cotton, rayon, ramie, jute, and flax and in the form of fiber, yarn, fabric or powder may be used in the process of this invention. The degree of crosslinking in the ion exchange powdered material diethylaminoethyl cellulose can also be increased by the process of this invention.

The following examples illustrate but do not limit the scope of this invention. Breaking strength tests were carried out according to the ASTM Method D1682-64. Condition wrinkle recovery measured were determined according to the ASTM D129'5-67 method and the wet recovery measurements according to the method described by Fujimoto, R. A., et al. (American Dyestuff Reptn, 52, 3219, 196 3).

EXAMPLE 1 Cotton printcloth, treated to contain 0.50% nitrogen in the form of diethylaminoethyl cellulose, soaked in various acids to insure that the amine was in the acid form, washed free of unbound acid, was padded with a 10% aqueous solution of dimethylolethylene urea [1,3- bis(hydroxymethyl)-2-imidazolidinone.. The fabric was dried at 60 C. for 7 minutes and cured at 160 C. for 3, minutes. After curing the fabric was washed free of non bound reagent and air dried. The following table summarizes results of properties measured in cured fabric.

Wrinkle recovery Nitrogen Formal- (W plus F), degrees added, dehyde Breaking Elon- As sociated weight, weight, Condistrength, gation, acld percent percent Wei; 1 tioned 1 pounds percent M.S.

2. 76 2. 36 222 (56) 280 (88) 29 9 0. l6 2. 43 2. 95 236 (77) 279 (89) 28 8 0. l4 3. 42 2. 01 247 (63) 304 (120) 0. 20 2. 14 2. 238 (74) 285 (74) 28 8 0. 13 2. 08 3. 67 231 (64) 281 (84) 27 8 0. 12 l. 90 3. 15 216 (48) 277 (73) 29 8 0. 11 1. 89 2. 97 200 (33) 271 (75) 28 9 0. 11 1. 58 2. 67 218 (47) 289 29 9 0. 09 l. 89 3. 25 241 (71) 280 (75) 29 8 0. l1

1 Bracketed numbers represent the increase in wrinkle recovery with respect to each control fabric (DEAEHX).

2 M.S. represents molar substitution based on nitrogen added to the fabric by DMEU treatment and based on one DMEU unit per crosslink.

3 EXAMPLE 2 Diethylaminoethyl cotton of 0.9% nitrogen in the hydrochloride form is padded with a aqueous solution of dimethylolethylene urea; dried at C. for 7 minutes and cured at various temperatures for 3 minutes. Results of treated fabrics shown below.

Wrinkle recovery Nitrogen Formal- (W plus F), degrees added, dehyde Breaking Elon- Weight, weight, Condistrength, gation, percent percent Wet tioned pounds percent M.S.

Cure temperature, 0.:

100.. 0. 47 0. 89 196 217 41 14 025 0. 84 1. 67 205 234 38 14 050 1. 23 2. 47 231 254 33 12 070 130.- 1. 66 2. 57 234 280 28 14 095 1. 67 3. 26 252 273 27 13 095 1. 75 3. 29 267 287 25 13 100 1. 79 2. 69 266 297 21 13 105 1. 67 2. 91 267 293 22 16 095 DEAE contr0l 0.94 194 155 37 22 1 MS. represents molar substitution based on nitrogen added to fabric by DMEU treatment and based on one DMEU unit per crosslink.

EXAMPLE 3 Diethylaminoethyl cotton of 0.5% nitrogen in the hydrochloride form is padded with various concentrations of dimethylolethyleneurea, dried 7 minutes at 60 C. and cured at 160 C. for 3 minutes. Results obtained are listed below.

Wrinkle recovery 1 M.S. based on nitrogen added to fabric by DMEU treatment and based on one DMEU unit per crosslink.

Diethylaminoethyl cotton of varying nitrogen content and in the hydrochloride form is padded with a 10% aqueous solution of dimethylolethylene urea, dried 60 C. for 7 minutes, and cured at 160 C. for 3 minutes. Results obtained are summarized below.

Wrinkle recovery droxymethy1)-2(IH)-tetrahydropyrimidinone; (3) dihydroxyethyleneurea (DHEU), 4,5-dihydroxy-2-imidazolidinone, and (4) dimethyldihydroxyethyleneurea (DMe- DHEU), 1,3-bisdimethyl-4,5-dihydroxy-Z-imidazolidinone, (5) dimethyloldihydroxyethyleneura (DMDHEU). 1,3- bis(hydroxymethyl) 4,5 dihydroxy-2-imidazolidinone. Each is dried at 60 C. for 7 minutes and cured at 160 C. for 5 minutes. Results obtained are summarized below.

Diethylaminoethyl cotton of 0.2% nitrogen in the hydrochloride form is padded to 100% wet pickup with a 10% aqueous dimethylolethyleneurea solution, dried at 60 for 7 minutes. The fabric is allowed to stand at room temperature in this condition until ready for curing. At various intervals portions of fabric are removed. They are tested for nitrogen and crease recovery. At the same p i t Nitaoigedn rz or ma ldegrees time, another portion is cured at 160 C. for 3 minutes. Or ginalni rogen a e e y e 50 eontent,Weight, Weight Weight, Condi- Results are tabulated below percent percent percent Wet tioned M.S l

1. 25 1. 83 216 212 o. 07 1. 28 1. 87 221 239 0.07 Percent nitrogen 1. 07 1. 74 226 241 0.06 added Wrinkle recovery 1 17 1.88 223 256 0. 07 1 26 2.03 229 260 0.07 59 Before cure After cure 1.41 2. 81 256 272 0.08 Before After 1.70 2. 09 266 207 0.10 cure cure et Dry et Dry 1M.S. is molar substitution based on nitrogen added to fabric by Days delay DMEU treatment and based on one DMEU unit per crosslink. 0 0 1. 55 176 190 275 298 0.02 1.52 185 240 285 EXAMPLE 5 60 0.04 1.45 160 187 240 275 0 0.10 1.45 186 230 275 Diethylammoethyl cottons contamlng 0.5 nitrogen 1n the hydrochloride form are treated with 8% dimethylolethylene urea in various solvents, dried at 60 C. for 7 EXAMPLE 3 minutes, and cured at 160 C. for 3 minutes.

6o DEA E cotton in the hydrochloride form containing Wrinkle recovery Molar Condisubsti- Solvent Wet tion tutes l\ us 250 270 .08

90% dioxane plus 10% H20 265 282 09 00% EtOH plus 10% E 0 268 285 09 90% THF plus 10% E20. 270 290 125 98% methylene chloride plus 2% H20- 245 282 .05 1,3-dichloro-2-propanol 258 290 07 l-chloro-Z-propanol 250 283 04 0.77% N is padded twice to 100% wet pickup with an 8% aqueous solution of dimethyloldihydroxyethyleneurea (DMDHEU). It is dried at 60 C. for 7 minutes. The fabric is then allowed to remain under room conditions until curing is desired. A portion is removed, washed in cold then hot tap H 0 and ironed dry. At the same time, another portion is removed and cured at 160 C. for 3 minutes and then washed in hot tap H 0 and ironed dry. Results obtained after varying delay times are tabulated in the following table:

Before cure After cure- Percent Crease angle Percent Crease angle Percent formal- Percent formal- N added dehyde Wet Dry N added dchyde Wet Dry Delay (days):

EXAMPLE 9 (b) drying the treated fabric and (c) curing the dried fabric at an elevated temperature.

DEAE cotton in the hydrochloride form containing 0.77% N is padded twice to 100% wet pickup with a 10% aqueous solution of dimethylolmethylcarbamate. The fabric is dried at 60 C. for 7 minutes. The fabric is then allowed to remain under room conditions until curing is desired. At that time a portion is removed and washed in cold then hot tap H 0 and ironed dry. At the same time another portion is removed and cured at 160 C. for 3 minutes. It is then washed in hot tap H 0 and ironed dry. Results obtained after varying delay times are tabulated below.

Before cure- After cure- Percent Crease angle Percent Crease angle Percent formaldehyde Percent formal- N added added Wet Dry N added dehyde Wet Dry added Delay da s 7. The process of claim 1 wherein the N-methylol type compound is dimethylolmethyl carbamate.

References Cited UNITED STATES PATENTS 2,584,114 2/1952 Daul et al. 8116.3

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R. 

